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According to the U.S. Census Bureau, the county has a total area of 336 square miles (870 km2), of which 332 square miles (860 km2) is land and 3.7 square miles (9.6 km2) (1.1%) is water.[5] Webster County is part of the Western Coal Fields region of Kentucky.

There were 5,272 households out of which 27.2% had children under the age of 18 living with them, 55% were married couples living together, 10.8% had a female householder with no husband present, and 29.5% were non-families. 25.4% of all households were made up of individuals and 11.6% had someone living alone who was 65 years of age or older. The average household size was 2.51 and the average family size was 2.98.

In the county the population was spread out with 25.9% under the age of 19, 5.8% from 20 to 24, 25% from 25 to 44, 28.2% from 45 to 64, and 15.1% who were 65 years of age or older. The median age was 40.1 years. 49.7% of the population is male and 50.3% female.

The median income for a household in the county was $39,635, and the median income for a family was $49,580. Males employed full-time had a median income of $41,662 versus $26,502 for females. The per capita income for the county was $18,879. About 11.9% of families and 16% of the population were below the poverty line, including 21.9% of those under age 18 and 11.6% of those age 65 or over.